Polymeric reaction products of biphenols and organosilicon materials and method for making

ABSTRACT

Poly(silyloxytetraalkylbiphenyleneoxide)s are provided resulting from the reaction between a tetraalkylbiphenol, such as tetramethylbiphenol and an organosilicon material such as dimethyldichlorosilane or octamethylcyclotetrasilazane. The poly(silyloxytetraalkylbiphenyleneoxide)s are flame retardant film-forming materials useful as high performance injection moldable thermoplastic and dielectrics.

BACKGROUND OF THE INVENTION

This application is a continuation in part of copending application Ser.No. 07/353,713 filed May 18, 1989 and now abandoned.

The present invention relates to hydrolytically stablepoly(silyloxytetraalkylbiphenyleneoxide)s which are convertible intotransparent, flame retardant self-extinguishing films.

Prior to the present invention, as shown by Curry et al., for "SilanePolymers of Diols", Journal of Applied Polymer Science, Vol. 9, pp.295-311 (1965), various polymeric materials were prepared by reacting asilyl diamine with various organic diols such as biphenol. It was foundby Curry et al. that a polymer containing biphenyl linkages haddesirable properties. These materials were found to be stable up to 600°C. and fibers with fairly good tenacity (0.5 grams/den) could be drawndirectly and continuously from the polymer melt.

Organopolysiloxane-polyphenylene oxide block copolymers were made by theprocedure shown by Krantz, U.S. Pat. No. 3,668,273 by reactingpolyphenylene oxide segments with polydiorganosiloxane segmentsterminated with amine groups. These materials are useful in theformation of oriented films and fibers and as plasticizers forpolyphenylene oxide. An additional procedure for makingorganopolysiloxane-polyphenylene oxide block copolymers is shown byBostick et al., U.S. Pat. No. 3,522,326, which is directed to graftcopolymers useful for making molded, extruded, or otherwise shapedarticles, such as films and fibers having valuable mechanical andelectrical properties. Although the procedures of the prior art haveprovided a variety of silicone-aryleneoxy block copolymers havingvaluable thermoplastic properties and useful in a variety ofapplications, additional properties such as hydrolytic stability andflame retardance are required by the thermoplastic industry.

SUMMARY OF THE INVENTION

The present invention is based on the discovery that apoly(silyloxytetraalkylbiphenyleneoxide), made by condensingtetramethylbiphenol (TMBP) and a difunctional silane, such asdimethyldichlorosilane, has improved hydrolytic stability, and is highmolecular weight injection moldable material exhibiting flame resistantproperties and convertible to tough transparent flexible films atelevated temperature and pressure.

STATEMENT OF THE INVENTION

There is provided by the present inventionpoly(silyloxybiphenyleneoxide)s consisting essentially of chemicallycombined groups of the formula, ##STR1## where R is selected from thesame or different C.sub.(1-8) alkyl radicals, and R¹ is selected fromthe same or different C.sub.(1-13) monovalent hydrocarbon radicals andC.sub.(1-13) monovalent hydrocarbon radicals substituted with monovalentradicals inert during condensation.

In a further aspect of the present invention, there is provided a methodfor making poly(silyloxytetraalkylbiphenyleneoxide)s having chemicallycombined groups of formula (1) comprising,

(A) effecting reaction between a tetraalkylbiphenol of the formula,##STR2## and a difunctional organosilicon material selected from theclass consisting of a polyorganosilazane, a cyclopolyorganosilazane, andan organosilane of the formula, ##STR3##

(B) recovering the resulting poly(silyloxytetraalkylbiphenyleneoxide)from the mixture of (A), where R and R¹ are as previously defined, and Xis a hydrolyzable radical, and is preferably chloro.

Radicals included by R of formulas (1) and (2) are alkyl radicals, suchas methyl, ethyl, propyl, butyl, pentyl and hexyl; radicals included byR¹ are, for example, R radicals as previously defined, and substituted Rradicals, such as trifluoropropyl, cyanoalkyl, such as cyanoethyl andcyanopropyl; alkenyl radicals such as vinyl and propenyl; cycloaliphaticradicals, such as cyclopentyl, and cyclohexyl. R¹ also can be arylradicals, such as phenyl, xylyl, tolyl, naphthyl and anthryl; andhalogenated aryl radicals, such as chlorophenyl and bromo-tolyl, as wellas nitroaryl radicals, such as nitrophenyl and nitrotolyl.

Radicals included within X of formula (3) are for example halo, such aschloro, amino, amido, imido, ureido, alkoxy and acyloxy.

Some of the organosilazanes, including cyclopolyorganosilazanes whichcan be used in the practice of the present invention are difunctionalsilazanes shown by Martellock U.S. Pat. No. 3,243,404 and RochowChemistry of the Silicones, Second Edition 1951, John Wiley & Sons NewYork, Table 10, page 186 which are incorporated herein by reference. Forexample there can be used hexamethylcyclotrisilazane, andoctamethylcyclotetrasilazane.

Organosilanes which are included within formula (3) are for example##STR4##

In the practice of the present invention, thepoly(silyloxytetraalkylbiphenyleneoxide)s of formula (1) can be made bycondensing a tetraalkylbiphenol of formula (2), with the organosiliconmaterial. Depending upon the nature of the organosilicon material,condensation can be effected in the presence of an organic solvent,under neat conditions, and in the presence or absence of an acidacceptor. For example, if the organosilicon material is a halosilane,such as dimethyldichlorosilane, an organic solvent, such as toluene orortho-dichlorobenzene can be used in combination with an acid acceptor,such as triethylamine. In instances where a high boiling solvent isused, such as ortho-dichlorobenzene or chloronaphthalene, an acidacceptor is not necessary. High boiling solvent also can be used withorganosilazanes, or cycloorganosilazanes can be used as theorganosilicon material without a solvent under melt polymerizationconditions.

Suitable organic solvents which can be used in the practice of thepresent invention are for example, toluene, ortho-dichlorobenzene,chloro-naphthalene, and diphenylether.

Among the acid acceptors which can be used are, for example,triethylamine, dimethylbutylamine, N-methylpyrrolidine, andtrimethylamine. If desired, a chainstopper such as 2,6-xylenol can beintroduced to control the molecular weight of the polymer.

Recovery of the poly(silyloxytetraalkylbiphenyleneoxide) can be effectedby allowing the mixture to cool and pouring it into a precipitatingsolvent, such as isopropanol, or by removal from the reactor vessel inthe case of high solids or melt polymerization. The mixture can then befiltered and the product washed with additional organic solvent anddried at elevated temperatures.

The poly(silyloxytetraalkylbiphenyleneoxide)s of the present inventionhave been found to be flame retardant. These polymers can have amolecular weight in the range of 5,000 to 1,000,000. Thepoly(silyloxytetramethylbiphenyleneoxide)s have a Tg in the range ofabout 120° C. to 138° C. and a Tm of about 280° C. They can be blendedwith inert fillers, such as glass fiber, mica, clay, talc, titaniumdioxide and silica in a proportion of from 1 to 200 parts by weight offiller, per 100 parts of polymer.

In order that those skilled in the art will be better able to practicethe present invention, the following examples are given by way ofillustration and not by way of limitation. All parts are by weightunless otherwise indicated.

EXAMPLE 1

A mixture of 24.2 grams (0.100 mole) of tetramethylbiphenol (TMDP),12.89 grams (0.100 mole) of dimethyldichlorosilane and 300 ml. oforthodichlorobenzene was refluxed and stirred for 4 hours under anitrogen atmosphere and 0.05 mole HCl was discharged from the mixture.The temperature of the mixture rose from about 165° C. to about 180° C.The reaction mixture was then cooled to about 70° C., and 27.9 ml.(0.200 mole) of triethylamine was added. The mixture thickened slightlyafter the addition of the triethylamine and 0.1230 gram (0.5 molepercent) of 2,6-xylenol was added as a chainstopper. The reactionmixture was held at 70°-80° C. and another 5 grams ofdimethyldichlorosilane in 55 ml. of orthodichlorobenzene was added veryslowly. The solution became very viscous after 5 ml. of thedimethyldichlorosilane solution in orthodichlorobenzene was added. Thereaction mixture was then cooled to about 40° C. and poured slowly into3,000 ml. of isopropanol. A white fibrous solid precipitated from themixture. The product was collected and twice reslurried with 1,000 ml.of isopropanol. A filter cake of the product was collected after thefinal wash and pressed with dental dam to express as much solvent aspossible. The product was then dried at 140° C. in a vacuum oven for 4hours. There was obtained 26.5 grams (89%) yield of product. Based onmethod of preparation and GPC analysis, the product was a poly(dimethylsilyloxytetramethylbiphenyleneoxide) having a molecular weightof about 202,000. It had a Tg of 126° C. and T_(m) of 260° C. There wasobtained a transparent flexible film when the polymer was pressed at290° C. and a pressure of 1-2 tons for about 30 seconds. The product wasa useful dielectric material and found to be a flame resistant moldablethermoplastic.

EXAMPLE 2

A mixture of 300ml of ortho-dichlorobenzene, 24.2 grams (0.100 mole) oftetramethylbiphenol, 0.061 gram (0.0005 mole) of 2,6-xylenol and 21.8grams (0.215 mole) of triethylamine was heated under a nitrogenatmosphere at 80° C. and 12.89 grams (0.100 mole) ofdimethyldichlorosilane was added over a 10 minute period. The reactionmixture was then cooled and poured into 2,000 ml. of isopropanol toeffect precipitation of product. There was obtained a white fibroussolid which was reslurried with 2,000 ml. of isopropanol. The productwas then collected and pressed free of solvent with a dental dam. Theproduct was then dried in a vacuum oven at 130° C. for 3 days. There wasobtained 27.6 grams (92.6% yield) of a poly(dimethylsilyloxytetramethylbiphenyleneoxide) having a molecular weightof M(W)43,000. The polymer was molded in accordance with the method ofExample 1. There was obtained a transparent tough film useful as a flameretardant dielectric material.

EXAMPLE 3

There was added 103.2 parts of dimethyldichlorosilane to a solution at80° C. of 193.6 parts of tetramethylbiphenol and 240 parts oforthodichlorobenzene which had been dried by refluxing the mixture. Theresulting mixture was then refluxed under nitrogen and the HCl emissionwas monitored. After two hours, the temperature of the mixture was 193°C. and 50% of the HCl had been removed. After 6 hours, sufficientortho-dichlorobenzene was removed to obtain 80% solids and increase thereflux temperature. The reaction was continued for eleven hours beforeall of the HCl had been removed at 295° C. Excess dimethyldichlorosilanewas added to increase molecular weight. There was obtained a producthaving an Mn of 13,843 and an M(W) of 33,848. Its dispersivity was foundto be 2.45. Based on method of preparation and GPC analysis, the productwas an injection moldable poly(dimethylsilyloxytetramethylbiphenyleneoxide).

EXAMPLE 4

A mixture of 48.4 g of tetramethylbiphenol, 14.64 g ofoctamethycyclotetrasilazane and 50 ml of orthodichlorobenzene wasrefluxed under nitrogen. The emission of ammonia was monitored. Afterfive hours of reflux at 295° C. there was obtained a poly(dimethylsilyloxytetramethylbiphenyleneoxide) having a M(n) of 28,244, aM(W) of 87,286 and a dispersivity of 3.09. The MW of the polymer wasconfirmed by GPC.

In addition to the above examples showing polymeric reaction products ofbiphenols and organosilicon materials, a procedure for makingpolyphenylene ether-siloxane block copolymers is shown by McFarland, etal for Synthesis of Regulated Structure PolyphenyleneEther-Siloxane-Block Copolymers, Quarterly Progress Report, Feb. 1,1963-Apr. 3, 1963 of the Naugatuck Chemical Company of Naugatuck, Conn.which is incorporated herein by reference.

Percent "Char Yield" also has been identified as an important factor inthe evaluation of the flame retardance of polymeric reaction products ofbiphenols and organosilicon materials. As used hereinafter, Char Yieldmeans the weight % residue remaining upon termination of the completeburning of the polymeric reaction product being evaluated. Char Yieldcan be measured by weighing the % residue after complete burning of a1.5×0.5×1/16th inch molded sample of the polymeric reaction productplaced 2 inches from a radiant heat panel providing at least a 3.5watts/centimeter square heat flux. The % Char or Char Yield is done at aradiant heat source setting of 80 or 90 volts corresponding to 6.5-7.5watts/cm² heat flux depending upon what was needed to sustaincombustion.

In addition to formula 1, polymeric reaction products of biphenols andorganosilicon materials also were prepared consisting essentially ofchemically combined groups of the formula, ##STR5## by,

(C) effecting reaction between a biphenol of the formula,

    HO--R.sub.2 --OH                                           (5)

and a difunctional organosilicon material selected from the classconsisting of a polyorganosilazane, a cyclopolyorganosilazane, abisureidosilane, an α,ω bisaminopolysiloxane, and an organosilane offormula (3), and

(D) recovering from (C), the polymeric reaction product of the biphenoland difunctional organosilicon material, where R¹ is as previouslydefined, R² is a member selected from the class consisting of: ##STR6##R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ are members selected from the classconsisting of the same or different radicals consisting of hydrogen andC.sub.(1-13) monovalent hydrocarbon radicals included within R¹, Y is amember selected from the class consisting of --C(CH₃)₂ --, --CH₂ --,--SO₂ --, --S--, --O--, and n is an integer equal to 1 to 4 inclusive,or 2 to 4 inclusive.

EXAMPLES 5-8

In accordance with the procedure of Example 4, additionalpoly(organosiloxy biphenyleneoxide)s were prepared, except that in placeof tetramethylbiphenol, there was used biphenol,2,2'-di-t-butyldimethyl-6,6'-dimethyl-4, 4'-biphenol2,2'-dimethyl-4,4'-biphenol and 2,2'-dimethyl-4,4'-biphenol.

The polyorgano siloxy biphenyleneoxides were evaluated for T_(g), T_(m),OI, Char Yield, and Stability (TGA). They consisted essentially ofchemically combined groups of the formula, ##STR7## where R¹ is apreviously defined, R³, R⁴ and Y are shown below in Table 1, OI isOxygen Index, Me is methyl, t-Bu is tertbutyl, Ph is phenyl, TGA isThermographic Analysis and Char Yield is as previously defined:

                                      TABLE 1                                     __________________________________________________________________________                           TGA    Char Yield                                      Example                                                                            R.sup.3                                                                          R.sup.4                                                                          T.sub.g                                                                           T.sub.m                                                                           OI  Air/N.sub.2 (10%)                                                                    (Volts)                                         __________________________________________________________________________    4    Me Me 138° C.                                                                    280° C.                                                                    52.2%                                                                             440°/509° C.                                                           60(80)                                                                        47(87)                                          5    H  H   71° C.                                                                     -- 64.1%                                                                             550°/552° C.                                                           55(90)                                          6    t-Bu                                                                             Me --  250.sup.-                                                                         43.8%                                                                             330°/415° C.                                                           52(80)                                                         280°(d)                                                 7    Me H  113° C.                                                                     -- 60.3%                                                                             510°/550° C.                                                           51(90)                                          8    Ph H   85° C.                                                                     -- 53% 537°/559° C.                                                           52(90)                                          __________________________________________________________________________

EXAMPLES 9-15

There was added 9.4391 grams (0.03367 mols) of tetramethylbisphenol-A inincrements of 4.72 grams, 2.36 grams and 2.35 grams at half hourintervals using 10 ml dry toluene to transfer each addition to 7.82grams (0.03367 mols) of a 50% by weight toluene solution ofbis(trimethylureido)dimethyl silane maintained under a nitrogen blanketat a temperature of 78° C. The final solution had about 27% by weightsolids. The temperature of the resulting solution was raised to 120° C.one hour after the final tetramethylbisphenol-A addition to maintain thetoluene solution under reflux . The reaction was monitored by GPC. Themixture was refluxed for an additional hour. Apoly(tetramethylbisphenol-A monosiloxane) was obtained having a MW_(w)of 17,800. After the removal of some toluene to increase the percentsolids level, additional bisuriedo silane was added to provide a 7%excess. The reaction was left at reflux for two hours and an additional2.35 millimoles of bisuriedo silane was added to provide a 14% excesssilane. The reaction was continued for two hours diluted with tolueneand then cooled slightly prior to precipitation in isopropanol. Therewas obtained a polymer having MW_(w) of 56,500 and MW_(n) of 32,900 byGPC.

Following the above procedure additional poly(diaryloxy)monosiloxaneswere prepared. However a different disphenol was substituted for thetetramethylbisphenol-A. The poly(biphenol)monosiloxanes consistedessentially of chemically combined groups of the formula, ##STR8## whereR¹ is as previously defined and R⁵, R⁶ and Y are shown below in Table 2:

                                      TABLE 2                                     __________________________________________________________________________                                   TGA    Char Yield                              Example                                                                            Y    R.sup.5                                                                          R.sup.6                                                                          T.sub.g                                                                            T.sub.m                                                                            OI   Air/N.sub.2 (10%)                                                                    (Volts)                                 __________________________________________________________________________     9   C(CH.sub.3).sub.2                                                                  Me Me 97° C.                                                                      --   36   425°/470° C.                                                           33(80)                                  10   C(CH.sub.3).sub.2                                                                  H  H  119° C.                                                                     --   48   460°/450° C.                                                           31(80)                                  11   CH.sub.2                                                                           ME Me 69° C.                                                                      --   40.9 460°/445° C.                                                           40(80)                                  12   CH.sub.2                                                                           H  H  <38° C.                                                                     140°                                                                        --   500°                                                                          49(90)                                  13   SO.sub.2                                                                           Me Me 130° C.                                                                     --   25.4 335°/320° C.                                                           28(80)                                  14   S    Me Me 74° C.                                                                      141°,166°                                                            41   340°/370° C.                                                           --                                                           179°                                              15   S    H  H  <50°                                                                        --   <32  230° C.                                                                       45(80)                                  __________________________________________________________________________

EXAMPLES 16-18

Additional poly(tetramethylbiphenol)siloxanes were prepared by stirringa mixture at 70° C. using a nitrogen sparge consisting of 25.35grams(105 millimoles) of 2,6,2',6'-tetramethyl-4,4'biphenol and 25.3grams (93 millimoles) of1,3-dipyrrolidinyl-1,1,3,3-tetramethyldisiloxane. After stirring themixture for 2 hours, while continuously removing the pyrrolidinebyproduct, an additional 0.90 gram (3.3 millimole) of the disiloxane wasadded. The temperature was raised to 180° C. and after another 1 hour,another 0.90 gram (3.3 millimole) increment of the disiloxane was added.A final 0.90 gram increment of the disiloxane was added after anotherhour. The reaction mixture was then stirred at 180° C. for 15 hours.There was obtained a viscous polymer which was dissolved in chloroform,precipitated into a blender with methanol, redissolved in chloroform andreprecipitated into methanol to form a tacky viscous resin. There wasobtained a product which consisted essentially of chemically combinedgroups of the formula, ##STR9## where n is defined in Table 3 below, and"FOT" is Flame Out Time:

                                      TABLE 3                                     __________________________________________________________________________                               TGA    Char Yield                                  Example                                                                            [(CH.sub.3).sub.2 SiO1.sub.n ]                                                        Tg   OI  FOT  air/N.sub.2 (10%)                                                                    (Volts)                                     __________________________________________________________________________     1   n = 1   126° C.                                                                     52.5%                                                                             1.44 sec                                                                           465°/509° C.                                                           60-64(80)                                                138° C.                                                   16   n = 2    55° C.                                                                     44.1%                                                                             1.03 sec                                                                           460°/535° C.                                                           51.4(80)                                    17   n = 3    14° C.                                                                     --  --   440°/480° C.                                                           43.9(80)                                    18   n = 4   -16° C.                                                                     --  --   -/390° C.                                                                     41.7(90)                                    __________________________________________________________________________

Additional information about formula 8 polymers is as follows:

Example 16 poly(tetramethylbiphenol) disiloxane

Molecular Weight: M_(w) /M_(n) =54,000/26,300 IV: 0.48

Tensile Properties: 30% elongation; 2730 psi (1"/min)

Flexural Modulus: 160,000; 250,000 psi

²⁹ SiNMR: -14.2 ppm

¹³ C NMR: 150.8, 134.3, 128.5, 126.7, 17.6, -0.1 ppm

Example 17 poly(tetramethylbiphenol) trisiloxane

Molecular Weight: M_(w) /M_(n) =68,400/22,460 IV: 0.53

Tensile Properties: 309% elongation; 157 psi (2"/min)

²⁹ SiNMR: -14.9, -20.9 ppm

¹³ CNMR: 151.9, 134.3, 128.5, 126.7, 17.6, 0.7, -0.1 ppm

Example 18 poly(tetramethylbiphenol)tetrasiloxane IV: 0.19

Molecular Weight: M_(w) /M_(n) +30,000/14,000

²⁹ SiNMR: -14.9, -21.4 ppm

¹³ CNMR: 151.0, 134.4, 128.6, 126.8, 17.7, 1.0, 0.1 ppm

EXAMPLES 19-21

The procedure of examples 9-15 was repeated, except that bisphenols wereused, where Y in formula 6 is O, (example 19), ##STR10## (example 20),and 1,3 phenyl (example 21) and R⁵ and R⁶ are hydrogen. The followingresults were obtained:

                  TABLE 4                                                         ______________________________________                                        Ex-                                                                           am-                            Char        TGA(10%)                           ple  Y        R.sup.5                                                                             R.sup.6                                                                           T.sub.g /T.sub.m                                                                     Yield  OI   Air/N.sub.2                        ______________________________________                                        19   O        H     H   33°/--                                                                        41.5(90)                                                                             70.6 520/454° C.                 20   C(C Cl.sub.2)                                                                          H     H   78°/--                                                                        57.5(90)                                                                             64   423/417° C.                 21   1,3      H     H   95.5°/--                                                                      54.5(90)                                                                             44.5 578/530° C.                      phenyl                                                                   ______________________________________                                    

EXAMPLES 22-36

The procedure of 4 was repeated, except that in place oftetramethylbiphenol, there were used hydroquinone (example 22),2-methylhydroquinone (example 23), 2,3-dimethyl hydroquinone (example24), 2,3,5,6-tetramethylhydroquinone (example 25) 2-phenyl hydroquinone(example 26), resorcinol (example 27), 2-methyl resorcinol (example 28)4-ethyl resorcinol (example 29) 2,7 naphthalenediol (example 30), 1,5naphthalenediol (example 31) 1,4 naphthalenediol (example 32), 1,6naphthalenediol (example 33) 2,6 naphthalenediol (example 34), an equalmolar mixture of tetramethylbiphenol and tetramethylbisphenol-A (example35) and an equal molar mixture of tetramethylbiphenol and biphenol(example 36). The following results were obtained, where Char Yield isCY% and % Char is weight percent of polymer residue after the TGA wascompleted:

                  TABLE 5                                                         ______________________________________                                        Ex-           CHAR     CHAR                                                   am-           YIELD    YIELD        TGA                                       ple  T.sub.G /T.sub.M                                                                       (volts)  (700° N.sub.2)                                                                OI    air/N.sub.2 (10%)                         ______________________________________                                        22   -25°/                                                                           38(90)   26     62.6  485°/415° C.                     112°                                                              23   0.5/--   39(90)   33     56.3  436°/429° C.                24   19°/--                                                                          39.8(90) 48     62.   450°/470° C.                25   45/--    46(90)   43     48.5   438°/466° C.*              26   42.6°/--                                                                        46.5(90) 53     58.   460°/480° C.                27   -14°/--                                                                         12.3(90) 2.5    60.3   365°/410° C.**             28   3.5°/--                                                                         42.3(90) 34.5   53.   380°/455° C.                29   -14°/--                                                                         17.2(90) 16     49-57  313°/347° C.**             30   45°/--                                                                          52/62(90)                                                                              42     54.4. 560°/470° C.                31   61.7°/                                                                          52(90)   46     53.5. 557°/511° C.                     148°                                                              32   54°                                                                             39(90)   33     62.5  447°/454° C.                33   51°                                                                             49(90)   27     >72   557°/536° C.                34   54°                                                                             63/(90)  54     57.6  568°/484°  C.               35   109°/--                                                                         44(90)   47     49.3  445°/485° C.                36   94.5°/--                                                                        55.3(90) 58.5   54.4  485°/511° C.                ______________________________________                                         *partly crosslinked                                                           **MW.sub.w lowered an order of magnitude on standing (150K-15K)          

Although the above examples are directed to only a few of the very manyvariables which can be used in the practice of the present invention, itshould be understood that the present invention is directed to a muchbroader variety of polymeric reaction products of biphenols andorganosilicon materials and method for making such materials as setforth in the description preceding these examples.

What is claimed is:
 1. A method for making apoly(silyloxytetraalkylbiphenyleneoxide) having improved char yieldcomprising,(A) effecting reaction between a tetraalkylbiphenol of theformula, ##STR11## and a difunctional organosilicon material selectedfrom the class consisting of a polyorganosiliazane, acyclopolyorganosilazane, a bisureidosilane and an organosilane of theformula, ##STR12## (B) recovering the resultingpoly(silyloxytetraalkylbiphenyleneoxide) from the mixture of (A),where Ris selected from the same or different C.sub.(1-8) alkyl radicals, R¹ isselected from the same or different C.sub.(1-13) monovalent hydrocarbonradicals or C.sub.(1-13) monovalent hydrocarbon radicals substitutedwith monovalent radicals inert during condensation, and X is ahydrolyzable radical.
 2. A method in accordance with claim 1, where thetetraalkylbiphenol is tetramethylbiphenol.
 3. A method in accordancewith claim 1, where the difunctional organosilicon material isdimethyldichlorosilane.
 4. A method in accordance with claim 1, wherethe cyclopolyorganosilane is octamethylcyclotetrasilazane.
 5. A methodfor making polymeric reaction products comprising,(C) effecting reactionbetween a dihydric phenol of the formula,

    HO--R.sub.2 --OH

and a difunctional organosilicon material selected from the classconsisting of a polyorganosilazane, a cyclopolyorganosilazane, abisureidosilane an α, ω bisaminopolysiloxane and an organosilane of theformula, ##STR13## (D) recovering the polymeric reaction product from(C), wherein R¹ is selected from the same or different C.sub.(1-13)monovalent hydrocarbon radicals, or C.sub.(1-13) monovalent hydrocarbonradicals substituted with monovalent radicals inert during condensation,R² is a member selected from the class consisting of, ##STR14## R³, R⁴,R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰ are members of a class selected from the sameor different C.sub.(1-13) monovalent hydrocarbon radicals, Y is a memberselected from the class consisting of --C(CH₃)₂ --, --CH₂ --, --SO₂ --,--S--, --O--, ##STR15##
 6. A method in accordance with claim 5, wherethe dihydric phenol is, ##STR16## and R is the same or different,C.sub.(1-8) alkyl radicals
 7. A method in accordance with claim 5, wherethe difunctional organosilican material is a cyclopolyorganosilazane. 8.A method in accordance with claim 5, where the difunctionalorganosilican material is a bisureidosilane.
 9. A polymeric reactionproduct of a dihydric phenol and an organosilicon material consistingessentially of chemically combined groups of the formula, ##STR17##where R¹ is selected from the same or different C.sub.(1-13) monovalenthydrocarbon radicals, or C.sub.(1-13) monovalent hydrocarbon radicalssubstituted with monovalent radicals inert during condensation, R² is amember selected from the class consisting of, ##STR18## Y is a memberselected from the class consisting of --C(CH₃)₂ --, --CH₂ --, --SO₂ --,--S--, --O--, ##STR19## R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰ are membersor a class selected from the same or different C.sub.(1-13) monovalenthydrocarbon radicals, and n is an integer equal to 1 to 4 inclusive. 10.Poly(silyloxytetraalkylbiphenyleneoxide)s consisting essentially ofchemically combined groups of the formula ##STR20## where R is selectedfrom the same or different C.sub.(1-8) alkyl radicals, R¹ is selectedfrom the same or different C.sub.(1-13) monovalent hydrocarbon radicals,or C.sub.(1-13) monovalent hydrocarbon radicals substituted withmonovalent radicals inert during condensation. 11.Poly(biphenol)monosiloxanes consisting essentially of chemicallycombined groups of the formula, ##STR21## where R¹ is selected from thesame or different C.sub.(1-13) monovalent hydrocarbon radicals, orC.sub.(1-13) monovalent hydrocarbon radicals substituted with monovalentradicals neutral during equilibration, R⁵ and R⁶ are members of a classselected from the same or different C.sub.(1-13) monovalent hydrocarbonradicals, and Y is a member selected from the class consisting of--C(CH₃)₂ --, --CH₂ --, --SO₂ --, --S--, --O--, ##STR22## 12.Poly(hydroquinone monosiloxane)s consisting essentially of chemicallycombined groups of the formula, ##STR23## where R¹ is selected from thesame or different C.sub.(1-13) monovalent hydrocarbon radicals, orC.sub.(1-13) monovalent hydrocarbon radicals substituted with monovalentradicals insert during condensation and R⁷ and R⁸ are members or a classselected from the same or different C.sub.(1-13) monovalent hydrocarbonradicals.
 13. Poly(resorcinol monosiloxane)s consisting essentially ofchemically combined groups of the formula, ##STR24## where R¹ isselected from the same or different C.sub.(1-13) monovalent hydrocarbonradicals, or C.sub.(1-13) monovalent hydrocarbon radicals substitutedwith monovalent radicals inert during condensation and R⁹ and R¹⁰ aremembers or a class selected from the same or different C.sub.(1-13)monovalent hydrocarbon radicals.
 14. Poly(binaphthol monosiloxane)shaving the formula, ##STR25## where R¹ is selected from the same ordifferent C.sub.(1-13) monovalent hydrocarbon radicals, or C.sub.(1-13)monovalent hydrocarbon radicals substituted with monovalent radicalsinert during condensation.
 15. Poly (tetraorganobiphenol) siloxanesconsisting essentially of chemically combined groups of the formula,##STR26## where R¹ is selected from the same or different C.sub.(1-13)monovalent hydrocarbon radicals, or C.sub.(1-13) monovalent hydrocarbonradicals substituted with monovalent radicals inert during condensationand R³ and R⁴ are members of a class selected from the same or differentC.sub.(1-13) monovalent hydrocarbon radicals and n is an integer equalto 1 to 4 inclusive.
 16. Poly(silyloxytetraalkylbiphenyleneoxide)s inaccordance with claim 10, where R and R¹ are methyl.
 17. Apoly(dimethylsilyloxytetramethylbiphenyleneoxide).